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Catalyst layers in proton exchange membrane fuel cells consist of platinum-group-metal nanocatalysts supported on carbon aggregates, forming a porous structure through which an ionomer network percolates. The local structural character of these heterogeneous assemblies is directly linked to the mass-transport resistances and subsequent cell performance losses; its three-dimensional visualization is therefore of interest. Herein we implement deep-learning-aided cryogenic transmission electron tomography for image restoration, and we quantitatively investigate the full morphology of various catalyst layers at the local-reaction-site scale. The analysis enables computation of metrics such as the ionomer morphology, coverage and homogeneity, location of platinum on the carbon supports, and platinum accessibility to the ionomer network, with the results directly compared and validated with experimental measurements. We expect that our findings and methodology for evaluating catalyst layer architectures will contribute towards linking the morphology to transport properties and overall fuel cell performance.

Water management by gas diffusion electrodes is a fundamental aspect of the performance of electrochemical cells. Herein, we introduce the characteristic constrictions size as a descriptor for microporous layers (MPL). This parameter is calculated by volumetric analysis of focused ion beam nanotomography and compared to mercury intrusion porosimetry measurements.

The surface wettability of catalysts is typically controlled via surface treatments that promote catalytic performance. Here we report on potential-regulated hydrophobicity/hydrophilicity at cobalt-based oxide interfaces with an alkaline solution. The switchable wetting of single particles, directly related to their activity and stability towards the oxygen evolution reaction, was revealed by electrochemical liquid-phase transmission electron microscopy. Analysis of the movement of the liquid in real time revealed distinctive wettability behaviour associated with specific potential ranges. At low potentials, an overall reduction of the hydrophobicity of the oxides was probed. Upon reversible reconstruction towards the surface oxyhydroxide phase, electrowetting was found to cause a change in the interfacial capacitance. At high potentials, the evolution of molecular oxygen, confirmed by operando electron energy-loss spectroscopy, was accompanied by a globally thinner liquid layer. This work directly links the physical wetting with the chemical oxygen evolution reaction of single particles, providing fundamental insights into solid–liquid interfacial interactions of oxygen-evolving oxides., Surface treatments can tune catalysts’ wettability, which can be used to promote their catalytic performance. Now, a potential-dependent dynamic wetting behaviour of cobalt-based oxide catalysts is identified before and during the oxygen evolution reaction.

Liquid-phase transmission electron microscopy (LPTEM) is an essential tool for studying the dynamics of materials interactions at the nanoscale, in and/or with their operational environment. Microfabricated SiNx membrane cells further allow the integration of thin-film electrodes that opens the technique to studies of heterogeneous electrocatalysts under relevant electrochemical conditions. However, experiments remain challenging and the characteristics of the dedicated electrochemical cells and of the interactions of the electron beam with the liquid electrolyte demand careful interpretation of the results. Herein, we discuss important aspects that concern the implementation of electrochemical LPTEM (ec-LPTEM). We first consider the range of information that can be accessible with the technique for electrocatalytic applications and we detail the influence of the thickness and flow of liquid electrolytes using membrane-based microcells. Further, we provide guidelines pertinent to the electrochemical configuration of the substrate working, reference, and counter electrodes. We validate these considerations by experimentally demonstrating the application of ec-LPTEM for the CO2 reduction reaction (CO2RR), the oxygen reduction reaction (ORR), and the oxygen evolution reaction (OER). The probed effects in metallic and oxide catalysts are directly related to the applied electrochemical stimuli and corroborate the representativity of the processes under investigation following the considerations described herein.

Achieving an efficient and stable oxygen evolution reaction (OER) in an acidic or neutral medium is of paramount importance for hydrogen production via proton exchange membrane water electrolysis (...

Tailoring the surface properties of 2D materials, such as transition metal dichalcogenides (TMDCs), at the nanoscale is becoming essential in the fabrication of various 2D material-based nanoelectronic devices. Due to the chemical inertness of their basal plane, the surface modification of 2D TMDCs is limited to their defective sites, often requiring special treatments, such as the conversion of the TMDC from its semiconducting into its metallic phase. In this work, we show that the basal plane of a semiconducting 2D TMDC, molybdenum disulfide (MoS2) can be modified electrochemically by electrografting of aryl-diazonium salt. To demonstrate the advantages of this method at the nanoscale, we perform electrografting of 3, 5-bis(trifluoromethyl)benzenediazonium tetrafluoroborate on predefined MoS2 nanoribbons by addressing them individually via a different electrode. The ability to selectively address individually contacted 2D layers opens the possibility for specific surface modification of neighboring 2D nanostructures by different functional groups. This method could be extended to other aryl-diazonium compounds, and other 2D semiconducting materials.

Size, morphology, and surface sites of electrocatalysts have a major impact on their performance. Understanding how, when, and why these parameters change under operating conditions is of importance for designing stable, active, and selective catalysts. Herein, we study the reconstruction of a Cu-based nanocatalysts during the startup phase of the electrochemical CO2 reduction reaction by combining results from electrochemical in situ transmission electron microscopy with operando X-ray absorption spectroscopy. We reveal that dissolution followed by redeposition, rather than coalescence, is the mechanism responsible for the size increase and morphology change of the electrocatalyst. Furthermore, we point out the key role played by the formation of copper oxides in the process. Understanding of the underlying processes opens a pathway to rational design of Cu electro (re)deposited catalysts and to stability improvement for catalysts fabricated by other methods.

Among the perovskites used to catalyze the oxygen evolution reaction (OER), Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) exhibits excellent activity which is thought to be related to dynamic reconstruction at t...

Complex oxides show extreme sensitivity to structural distortions and defects, and the intricate balance of competing interactions which emerge at atomically defined interfaces may give rise to unexpected physics. In the interfaces of non-magnetic complex oxides, one of the most intriguing properties is the emergence of magnetism which is sensitive to chemical defects. Particularly, it is unclear which defects are responsible for the emergent magnetic interfaces. Here, we show direct and clear experimental evidence, supported by theoretical explanation, that the B-site cation stoichiometry is crucial for the creation and control of magnetism at the interface between non-magnetic ABO3-perovskite oxides, LaAlO3 and SrTiO3. We find that consecutive defect formation, driven by atomic charge compensation, establishes the formation of robust perpendicular magnetic moments at the interface. Our observations propose a route to tune these emerging magnetoelectric structures, which are strongly coupled at the polar-nonpolar complex oxide interfaces., In the interfaces of non-magnetic complex oxides, it is unclear which defects are responsible for the magnetic interfaces. Here, the authors find the B-site cation stoichiometry is crucial for the creation and control of magnetism at the interface between non-magnetic ABO3-perovskite oxides.

Ferroelectric materials, upon electric field biasing, display polarization discontinuities known as Barkhausen jumps, a subclass of a more general phenomenon known as crackling noise. Herein, we follow and visualize in real time the motion of single 90° needle domains induced by an electric field applied in the polarization direction of the prototypical ferroelectric BaTiO_{3}, inside a transmission electron microscope. The nature of motion and periodicity of the Barkhausen pulses leads to distinctive interactions between domains forming a herringbone pattern. Remarkably, the tips of the domains do not come into contact with the body of the perpendicular domain, suggesting the presence of strong electromechanical fields around the tips of the needle domains. Additionally, interactions of the domains with the lattice result in relatively free movement of the domain walls through the dielectric medium, indicating that their motion-related activation energy depends only on weak Peierls-like potentials. Control over the kinetics of ferroelastic domain wall motion can lead to novel nanoelectronic devices pertinent to computing and data storage applications.

Water management by gas diffusion media and electrodes is a fundamental aspect of the performance of electrochemical cells including proton exchange membrane (PEM) fuel cells. In these devices, product liquid water blocks part of the available space for reactants flow, leading to mass transport losses and lowering of the performance1. Pores saturation has been observed with different experimental techniques for GDL substrates, however a detailed saturation process at the pore size scale of the microporous layer (MPL) is necessary. Previously, it was suggested that large pore network domains are responsible for an enhanced water evacuation2, however, possible existence of narrow size constrictions could still limit water evacuation. In this work, we detail the benefits of three-dimensional imaging of the pore network at the typical MPL pore size scale, i.e. the sub-micrometre scale, which is achieved by focused ion beam scanning electron microscope (FIB-SEM) nanotomography. Two different MPL designs were analysed: an acetylene black based MPL, named Li100, and a vapor grown carbon fiber (VGCF) based MPL, the latter showing better performance under high relative humidity conditions2, 3. FIB-SEM tomography volumes in Fig. 1a-b were used to observe the relative distribution of larger pore domains and narrower pore constrictions. By removing narrower sized pores from the network and analysing the connections of large pore domains, we show the existence of a characteristic size for pore constrictions below which the pore network is well connected. This characteristic size is depicted by the red line in Fig. 1c-d, which plots the fraction of connected pores as a function of their minimum size. Constrictions size values for the two MPL designs were further validated with mercury intrusion experiments, since constrictions affect all the intrusions by capillary pressure, such as water flow in hydrophobic MPLs. The calculated parameters, which are representative of the connections between large pore domains, open up new perspectives on the prediction of gas diffusion under realistic conditions. The approach allows evaluation of the effects of alternatively removing larger and narrower pore domains, to understand the saturation-driven tortuosity in different MPL structures. J. Shen, L. Xu, H. Chang, Z. Tu, and S. H. Chan, Energy Conversion and Management, 207, 112537 (2020). C. Simon, D. Kartouzian, D. Müller, F. Wilhelm, and H. A. Gasteiger, Journal of The Electrochemical Society, 164, F1697–F1711 (2017). C. Simon, J. Endres, B. Nefzger-Loders, F. Wilhelm, and H. A. Gasteiger, Journal of The Electrochemical Society, 166, F1022–F1035 (2019). Figure 1

ConspectusIn this Account, we describe the challenges and promising applications of transmission electron microscopy (TEM) imaging and spectroscopy at cryogenic temperatures. Our work focuses on two areas of application: the delay of electron-beam-induced degradation and following low-temperature phenomena in a continuous and variable temperature range. For the former, we present a study of LiMn

Perovskites have been widely studied for electrocatalysis due to the exceptional activity they exhibit for surface-mediated redox reactions. To date, descriptors based on density functional theory calculations or experimental measurements have assumed a bulk-like configuration for the surfaces of these oxides. Herein, we probed an initial exposed surface and the screened subsurface of LaMnO3 particles, demonstrating that their augmented activity toward the oxygen reduction reaction (ORR) can be related to a spontaneous surface reconstruction. Our approach involves high energy resolution electron energy loss spectroscopy for the fine structure probing of oxygen and manganese ionization edges under electron beam conditions that leave the structure unaffected. Atomic multiplet and density functional theory calculations were used to compute the theoretical energy loss spectra for comparison to the experimental data, allowing to quantitatively demonstrate that the particle surface layers are La-deficient. This deficiency is linked to equivalent tetrahedral Mn2+ sites at the reconstructed surface, leading to the coexistence of +3 and +2 oxidation states of Mn at the surface layers. This electronic and structural configuration of the as-synthesized particles is indirectly linked to strong adsorption pathways that promote the ORR on LaMnO3, and thus, it could prove to be a valuable design feature in the engineering of catalytic surfaces.

Phosphorene is a mono-elemental, two-dimensional (2D) substance with outstanding, highly directional properties and a bandgap that depends on the number of layers of the material1–8. Nanoribbons, meanwhile, combine the flexibility and unidirectional properties of one-dimensional nanomaterials, the high surface area of 2D nanomaterials and the electron-confinement and edge effects of both. The structures of nanoribbons can thus lead to exceptional control over electronic band structure, the emergence of novel phenomena and unique architectures for applications5,6,9–24. Phosphorene’s intrinsically anisotropic structure has motivated numerous theoretical calculations of phosphorene nanoribbons (PNRs), predicting extraordinary properties5,6,12–24. So far, however, discrete PNRs have not been produced. Here we present a method for creating quantities of high-quality, individual PNRs by ionic scissoring of macroscopic black phosphorus crystals. This top–down process results in stable liquid dispersions of PNRs with typical widths of 4–50 nm, predominantly single-layer thickness, measured lengths of up to 75 μm and aspect ratios of up to 1,000. The nanoribbons are atomically flat single crystals, aligned exclusively in the zigzag crystallographic orientation. The ribbons have remarkably uniform widths along their entire lengths, and are extremely flexible. These properties—together with the ease of downstream manipulation via liquid-phase methods—should enable the search for predicted exotic states6,12–14,17–19,21, and an array of applications in which PNRs have been predicted to offer transformative advantages. These applications range from thermoelectric devices to high-capacity fast-charging batteries and integrated high-speed electronic circuits6,14–16,20,23,24. Phosphorene nanoribbons are produced in liquids through the intercalation of black phosphorous crystals with lithium ions, enabling the search for predicted exotic states and applications of these nanoribbons.

A microporous layer (MPL) is typically added to the gas diffusion layer of polymer electrolyte fuel cells (PEFCs) to promote cell performance and water management. The transport mechanism of the water through the MPL is, however, not well understood due to its small pores (20-500 nm). Here, we demonstrate that polychromatic X-ray tomographic microscopy (XTM) can be used to determine the porosity and the spatial distribution of water in nanoporous materials and can quantitatively map the liquid water saturation of MPLs. The presented technique requires no a priori knowledge of the composition of the MPL and has a field of view on the millimeter scale, which is orders of magnitude larger than conventional electron microscopy techniques for nanoscale materials. The available field of view is compatible with existing operando cells for X-ray tomography, paving the way for the analysis of water transport in MPLs during operation.

Phosphorene nanoribbons (PNRs) have been widely predicted to exhibit a range of superlative functional properties; however, because they have only recently been isolated, these properties are yet to be shown to translate to improved performance in any application. PNRs show particular promise for optoelectronics, given their predicted high exciton binding energies, tunable bandgaps, and ultrahigh hole mobilities. Here, we verify the theorized enhanced hole mobility in both solar cells and space-charge-limited-current devices, demonstrating the potential for PNRs improving hole extraction in universal optoelectronic applications. Specifi- cally, PNRs are demonstrated to act as an effective charge-selective interlayer by enhancing hole extraction from polycrystalline methylammonium lead iodide (MAPbI(3)) perovskite to the poly(triarylamine) semiconductor. Introducing PNRs at the hole-transport/MAPbI(3) interface achieves fill factors above 0.83 and efficiencies exceeding 21% for planar p-i-n (inverted) perovskite solar cells (PSCs). Such efficiencies are typically only reported for single-crystalline MAPbI(3)-based inverted PSCs. Methylammonium-free PSCs also benefit from a PNR interlayer, verifying applicability to architectures incorporating mixed perovskite absorber layers. Device photoluminescence and transient absorption spectroscopy are used to demonstrate that the presence of the PNRs drives more effective carrier extraction. Isolation of the PNRs in space-charge-limited-current hole-only devices improves both hole mobility and conductivity, demonstrating applicability beyond PSCs. This work provides primary experimental evidence that the predicted superlative functional properties of PNRs indeed translate to improved optoelectronic performance.

In situ scanning transmission electron microscopy enables observation of the domain dynamics in ferroelectric materials as a function of externally applied bias and temperature. The resultant data sets contain a wealth of information on polarization switching and phase transition mechanisms. However, identification of these mechanisms from observational data sets has remained a problem due to a large variety of possible configurations, many of which are degenerate. Here, we introduce an approach based on rotationally invariant variational autoencoder (VAE), which enables learning a latent space representation of the data with multiple real-space rotationally equivalent variants mapped to the same latent space descriptors. By varying the size of training sub-images in the VAE, we tune the degree of complexity in the structural descriptors from simple domain wall detection to the identification of switching pathways. This yields a powerful tool for the exploration of the dynamic data in mesoscopic electron, scanning probe, optical, and chemical imaging. Moreover, this work adds to the growing body of knowledge of incorporating physical constraints into the machine and deep-learning methods to improve learned descriptors of physical phenomena., Minor updates (affiliations, abstract, data statement)

We report on the electric field response of 180 degree nanodomain walls in BaTiO$_3$ using in situ electrical biasing in transmission electron microscopy (TEM). The sample is biased on a micro-device designed for reliable testing whose key attributes are confirmed by finite element calculations. The presence of weakly charged zig-zag domain walls at room temperature is attributed to the geometric confinement of the device. The motion of the domain walls under the applied electric field allows to extract local P-E loops where distinct domain wall pinning in deep and random energy potential profiles, characteristic for hard and soft ferroelectrics, respectively, are observed. Hard domain wall pinning results in asymmetrical loops typical for "hard" ferroelectrics while the soft domain wall pinning follows Rayleigh-like behaviour. All effects are measured locally and directly from the imaged domain structure.

Among the perovskites used to catalyze the oxygen evolution reaction (OER), Ba

Size, morphology, and surface sites of electrocatalysts have a major impact on their performance. Understanding how, when, and why these parameters change under operating conditions is of importance for designing stable, active, and selective catalysts. Herein, we study the reconstruction of a Cu-based nanocatalysts during the startup phase of the electrochemical CO

A three-dimensional finite element method (FEM) model simulating the electrochemical behaviour of Pt coplanar thin-film electrodes used for liquid cell transmission electron microscopy measurements was developed. The model included reaction kinetics and it was applied for the oxygen evolution reaction (OER). Kinetic parameters of OER in the liquid cell were experimentally acquired and applied to the FEM model. Comparison between the experimental and simulated polarization curves demonstrated the reliability of the FEM predictions. The simulations were used to produce maps of the potential and current density distributions of the working and counter electrodes as well as for calculating the distribution of the current density in the liquid electrolyte. Two distinctive electrode geometries were evaluated with the FEM model. It was predicted that non-symmetrical electrode designs can cause unexpected electrochemical behaviour with respect to the electrolyte current density between working and counter electrodes accompanied by the presence of hot spots. The findings suggest that FEM simulations could be key to designing well-performing electrochemical microcells for liquid phase electron microscopy experiments.

Electrochemical liquid cell transmission electron microscopy (TEM) is a unique technique for probing nanocatalyst behavior during operation for a range of different electrocatalytic processes, including hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), or electrochemical CO2 reduction (eCO2R). A major challenge to the technique's applicability to these systems has to do with the choice of substrate, which requires a wide inert potential range for quantitative electrochemistry, and is also responsible for minimizing background gas generation in the confined microscale environment. Here, we report on the feasibility of electrochemical experiments using the standard redox couple Fe(CN)63-/4- and microchips featuring carbon-coated electrodes. We electrochemically assess the in situ performance with respect to flow rate, liquid volume, and scan rate. Equally important with the choice of working substrate is the choice of the reference electrode. We demonstrate that the use of a modified electrode setup allows for potential measurements relatable to bulk studies. Furthermore, we use this setup to demonstrate the inert potential range for carbon-coated electrodes in aqueous electrolytes for HER, OER, ORR, and eCO2R. This work provides a basis for understanding electrochemical measurements in similar microscale systems and for studying gas-generating reactions with liquid electrochemical TEM.

A multi-modal and multi-scale non-local means (M3S-NLM) method is proposed to extract atomically resolved spectroscopic maps from low signal-to-noise (SNR) datasets recorded with a transmission electron microscope. This method improves upon previously tested denoising techniques as it takes into account the correlation between the dark-field signal recorded simultaneously with the spectroscopic dataset without compromising on the spatial resolution. The M3S-NLM method was applied to electron energy dispersive X-ray and electron-energy-loss spectroscopy (EELS) datasets. We illustrate the retrieval of the atomic scale diffusion process in an Al1-xInxN alloy grown on GaN and the surface oxidation state of perovskite nanocatalysts. The improved SNR of the EELS dataset also allows the retrieval of atomically resolved oxidation maps considering the fine structure absorption edge of LaMnO3 nanoparticles. Ministry of Education (MOE) This work was supported by Ministry of Education Academic Research Fund Tier 1 grants RG101/17 (Nanyang Technological University). This research was supported under the Discovery Projects funding scheme (Project DP140102538) of the Australian Research Council and by the Alexander von Humboldt Foundation. The authors at AICES RWTH Aachen University were funded in part by the Excellence Initiative of the German Federal and State Governments through grant GSC 111.

Electrochemical liquid-phase transmission electron microscopy (TEM) is showing excellent promise in fundamental studies of energy-related processes including lithium-ion battery (LIB) cycling. A key requirement to accurately interpret the measurements and acquire quantitative information is the implementation of a reliable reference electrode. Quasi-reference electrodes (QRE) remain commonly used due to microfabrication constraints of the electrochemical cell, however, they typically yield dramatic potential drifts making the electrochemical results inconclusive. Here, we present a method of producing a stable and readily interpretable lithium-gold alloy micro-reference electrode, which exhibits a reference potential of 0.1 V vs Li/Li+. We first examine the feasibility of electrochemically alloying a pristine gold electrode, patterned on a chip for in situ TEM, using a benchtop setup, and investigate various sources to support the lithiation. We confirm the presence of the Li-Au alloy using chronopotentiometry (CP) and open circuit voltage (OCV) measurements, and by scanning electron microscopy (SEM), electron energy loss spectroscopy (EELS) and high-resolution (HR) TEM. Finally, we apply this methodology in situ and use LiFePO4 as a model cathode material to demonstrate the merit of the Li-Au alloy reference electrode for obtaining reproducible cyclic voltammetry (CV) measurements on a liquid cell microelectrode system.

Phosphorene is a mono-elemental, two-dimensional (2D) substance with outstanding, highly directional properties and a bandgap that depends on the number of layers of the material

A long-standing problem in the application of solid-state nanopores is the lack of the precise control over the geometry of artificially formed pores compared to the well- defined geometry in their biological counterpart, i.e. protein nanopores. To date, experimentally investigated solid-state nanopores have been shown to adopt approximately circular shape. A unique property of hexagonal boron nitride (h-BN) few-layers has been revealed by previous transmission electron microscopy (TEM) studies, where triangular defects or nanopores can be created or enlarged while maintaining their intrinsic triangular shape.1, 2 Here, we investigate the geometrical effect of the nanopore shape on ionic blockage induced by DNA translocation using triangular h-BN nanopores and approximately circular molybdenum disulfide (MoS2) nanopores. We observe a geometry-dependent ion scattering effect, which is further corroborated by a modified ionic blockage model. The well-acknowledged ionic blockage model is derived from uniform ion permeability through the 2D nanopore plane and hemisphere like access region in the nanopore vicinity.3, 4 Based on our experimental results, we propose a modified ionic blockage model, which is highly related to the ionic profile caused by geometrical variations. Our findings shed light on the rational design of 2D nanopores and should be applicable to arbitrary nanopore shapes.

The performance of complex oxide heterostructures depends primarily on the interfacial coupling of the two component structures. This interface character inherently varies with the synthesis method and conditions used since even small composition variations can alter the electronic, ferroelectric, or magnetic functional properties of the system. The focus of this article is placed on the interface character of a pulsed laser deposited CoFe2O4/BaTiO3 thin film. Using a range of state-of-the-art transmission electron microscopy methodologies, the roles of substrate morphology, interface stoichiometry, and cation intermixing are determined on the atomic level. The results reveal a surprisingly uneven BaTiO3 substrate surface formed after the film deposition and Fe atom incorporation in the top few monolayers inside the unit cell of the BaTiO3 crystal. Towards the CoFe2O4 side, a disordered region extending several nanometers from the interface was revealed and both Ba and Ti from the substrate were found to diffuse into the spinel layer. The analysis also shows that within this somehow incompatible composite interface, a different phase is formed corresponding to the compound Ba2Fe3Ti5O15, which belongs to the ilmenite crystal structure of FeTiO3 type. The results suggest a chemical activity between these two oxides, which could lead to the synthesis of complex engineered interfaces.

A primary method for the production of 2D nanosheets is liquid-phase delamination from their 3D layered bulk analogues. Most strategies currently achieve this objective by significant mechanical energy input or chemical modification but these processes are detrimental to the structure and properties of the resulting 2D nanomaterials. Bulk poly(triazine imide) (PTI)-based carbon nitrides are layered materials with a high degree of crystalline order. Here, we demonstrate that these semiconductors are spontaneously soluble in select polar aprotic solvents, that is, without any chemical or physical intervention. In contrast to more aggressive exfoliation strategies, this thermodynamically driven dissolution process perfectly maintains the crystallographic form of the starting material, yielding solutions of defect-free, hexagonal 2D nanosheets with a well-defined size distribution. This pristine nanosheet structure results in narrow, excitation-wavelength-independent photoluminescence emission spectra. Furthermore, by controlling the aggregation state of the nanosheets, we demonstrate that the emission wavelengths can be tuned from narrow UV to broad-band white. This has potential applicability to a range of optoelectronic devices.

In bulk composite materials, interfaces between adjacent materials can be neglected when evaluating the individual functional properties on the macroscopic scale. However, in nanostructured materials, what is described as an interfacial region can be a significant amount of the total volume of the composite. These interfaces are difficult to analyse by conventional TEM and XRD. Here we describe how a combination of material and property analyses provides evidence of microstructural arrangement on apparently epitaxial film interfaces on different substrates. CoFe2O4 films were grown on SrTiO3, LaAlO3, BaTiO3 and MgO single crystal substrates, all cut in 0 0 1 direction. Our analyses explain the importance of chemical stability of the interface, crystallographic matching between the magnetic film and the dielectric growth template and the different growth mechanisms. The microstructural features in films with thicknesses between 13 and 100 nm were identified. The large variation in the magnetic properties of the films demonstrates the importance of the interfacial chemistry on the final functional properties.

Doped SrTiO3 thin films, 55 nm thick, were epitaxially grown by Pulsed Laser Deposition with niobium contents ranging from 2 to 5 mol% on SrTiO3 and LaAlO3 substrates. The different templates result in different growth defects, film growth mechanism and therefore a different volume fraction of uniformly strained film under the critical thickness. The investigation of the conductivity reveals a significant difference between the two substrate choices, but only at elevated temperatures with conductivity values up to 30% larger for films on SrTiO3 substrates compared with LaAlO3. Whereas in bulk ceramics the niobium level dictates the total conductivity, here it was found that the substrate choice had a greater influence for thin films, in particular at temperatures over 400 C. This finding provides important information on conductive layers in complex heterostructures where strain and defects could work cooperatively. © 2013 Elsevier B.V. All rights reserved.

Understanding the interaction between water and oxides is critical for many technological applications, including energy storage, surface wetting/self-cleaning, photocatalysis and sensors. Here, we report observations of strong structural oscillations of Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) in the presence of both H2O vapour and electron irradiation using environmental transmission electron microscopy. These oscillations are related to the formation and collapse of gaseous bubbles. Electron energy-loss spectroscopy provides direct evidence of O2 formation in these bubbles due to the incorporation of H2O into BSCF. SrCoO3−δ was found to exhibit small oscillations, while none were observed for La0.5Sr0.5CoO3−δ and LaCoO3. The structural oscillations of BSCF can be attributed to the fact that its oxygen 2p-band centre is close to the Fermi level, which leads to a low energy penalty for oxygen vacancy formation, high ion mobility, and high water uptake. This work provides surprising insights into the interaction between water and oxides under electron-beam irradiation. Understanding interactions between water and oxides is crucial for energy storage and photocatalysis. The combined effect of water and electron irradiation on perovskite catalysts results in structural oscillation triggered by gaseous bubbles.

Surface enhanced Raman scattering (SERS) "hot spots" are the regions where the electromagnetic field is significantly enhanced, resulting in much greater SERS activity than other areas. Therefore, the engineering and characterization of "hot spots" have attracted much attention. Herein, we have synthesized nanoworms formed by connecting hollow gold nanospheres and investigated their composition as well as their SERS properties, including their potential for simultaneous analysis of multiple species. The three-dimensional nanostructures that led to different SERS activities were investigated using correlated optical/SERS and SEM imaging. Gold nanoworms with hollow nanosphere segments and partial tube formation were confirmed. All highly SERS-active structures were found to be three-dimensional arrays consisting of inter-/intrananoworm interactions; no individual nanospheres were found to give significant SERS signal under the experimental conditions. The major SERS contribution was found to be the electromagnetic coupling effect within the three-dimensional arrays and the localized surface plasmon resonance of the nanostructure was found to have a minimal effect. This study gives insight into the basis of enhancement for these nanoworm structures and adds to the growing body of evidence in relation to nanostructures and surface enhancement of Raman scattering. © 2011 American Chemical Society.

Catalytic activity of perovskites for oxygen reduction (ORR) was recently correlated with bulk d-electron occupancy of the transition metal. We expand on the resultant model, which successfully reproduces the high activity of LaMnO3 relative to other perovskites, by addressing catalyst surface morphology as an important aspect of the optimal ORR catalyst. The nature of reaction sites on low index surfaces of orthorhombic (Pnma) LaMnO3 is established from First Principles. The adsorption of O2 is markedly influenced by local geometry and strong electron correlation. Only one of the six reactions sites that result from experimentally confirmed symmetry-breaking Jahn-Teller distortions is found to bind O2 with an intermediate binding energy while facilitating the formation of superoxide, an important ORR intermediate in alkaline media. As demonstrated here for LaMnO3, rational design of the catalyst morphology to promote specific active sites is a highly effective optimization strategy for advanced functional ORR catalysts. © 2015 American Chemical Society.

The electrochemical behavior of silicon-based anodes in lithium-ion batteries can be largely influenced by the cut-off potentials. Due to the strongly sloped voltage profile of silicon, changes in the cut-off potentials highly impact the degree of lithiation, and thus the associated volume expansion of the Li-Si alloy.1 While the lithiation cut-off potential of silicon has been addressed in several studies by the groups of Obrovac and Dahn, who highlighted the relevance of the crystalline Li15Si4 phase that forms at potentials below 0.07 V vs. Li/Li+, the de-lithiation cut-off potential of silicon is less understood.2–4 Recently, Klett et al. discussed the beneficial effect of a limited delithiation cut-off potential on the capacity retention of NCM523/silicon-graphite full-cells.5 In the present study, we evaluate the impact of the delithiation cut-off potential on the silicon particle degradation. Building up on previous studies,5,6 our characterization is concerned with the underlying morphological changes the silicon particles undergo during repeated cycling, which ultimately affect the entire electrode integrity. To test this hypothesis, silicon-graphite composite electrodes with a practical areal capacity of ~1.8 mAh cm-2 were prepared, consisting of 35 wt% nanometer-sized silicon (~200 nm) and 45 wt% graphite (~20 µm). Vapor grown carbon fibers and lithiated poly(acrylic acid) binder accounted for the remaining 20 wt%. Utilizing SiG//LiFePO4 Swagelok T-cells with a capacitively oversized positive electrode (~3.5 mAh cm-2) and a stable reference potential of ~3.45 V vs. Li/Li+, three cut-off conditions of the silicon-graphite electrodes, shown in Figure 1, were investigated. First, the silicon-graphite electrodes were fully lithiated to 0.01 V vs. Li/Li+ and completely delithiated to 1.25 V vs. Li/Li+ (brown curve). Second, we limited either the lithiation cut-off potential to 0.05 V vs. Li/Li+ (red curve) or, alternatively, the delithiation cut-off potential to 0.65 V vs. Li/Li+ (blue curve), with the latter two resulting in a capacity utilization of ~80%. By differential capacity analysis of selected galvano-static cycles we demonstrate that silicon-graphite electrodes with a limited delithiation cut-off potential of 0.65 V vs. Li/Li+ show less overpotential growth and significant improvement in capacity retention upon cycling. These observations are further supported by impedance spectroscopy at different states-of-charge using a gold-wire reference electrode to obtain individual impedance spectra from the positive and the negative electrode.7 Figure 1 . Voltage profiles of silicon-graphite electrodes (5th cycles) operated at different cut-off conditions. The data were obtained from SiG//LiFePO4 Swagelok-T cells with a gold-wire reference electrode that was sandwiched between two glass fiber separators soaked with an electrolyte of LP57 + 5 wt% FEC. Areal SiG capacity: ~1.8 mAh cm-2. The electrochemical results are complemented by transmission and scanning electron microscopy of the silicon particles and composite electrodes. The structural analysis indicates that the repeated delithiation of silicon particles to highly oxidative potentials (1.25 V vs. Li/Li+) causes dealloying reactions, which result in a roughening of the particle surface and the formation of highly porous structures, leading to significantly increased irreversible capacity losses and electrode polarization. Finally, a comparison of the different cut-off conditions and a proposal for an improved cycling protocol for silicon-graphite electrodes are discussed. References: (1) Obrovac, M. N.; Chevrier, V. L. Chem. Rev. 2014, 114, 11444–11502. (2) Obrovac, M. N.; Christensen, L. Electrochem. Solid-State Lett. 2004, 7 (5), A93–A96. (3) Li, J.; Dahn, J. R. J. Electrochem. Soc. 2007, 154 (3), A156. (4) Iaboni, D. S. M.; Obrovac, M. N. J. Electrochem. Soc. 2016, 163 (2), 255–261. (5) Klett, M.; Gilbert, J. A.; Pupek, K. Z.; Trask, S. E.; Abraham, D. P. J. Electrochem. Soc. 2017, 164 (1), 6095–6102. (6) Wetjen, M.; Jung, R.; Pritzl, D.; Gasteiger, H. A. ECS Meet. 230 2016, Abstr. #280. (7) Solchenbach, S.; Pritzl, D.; Kong, E. J. Y.; Landesfeind, J.; Gasteiger, H. A. J. Electrochem. Soc. 2016, 163 (10), A2265–A2272. Acknowledgements: The German Federal Ministry for Economic Affairs and Energy is acknowledged for funding (“LiMo” project with funding number 03ET6045D). Figure 1

Strategies for forming liquid dispersions of nanomaterials typically focus on retarding reaggregation, for example via surface modification, as opposed to promoting the thermodynamically driven dissolution common for molecule-sized species. Here we demonstrate the true dissolution of a wide range of important 2D nanomaterials by forming layered material salts that spontaneously dissolve in polar solvents yielding ionic solutions. The benign dissolution advantageously maintains the morphology of the starting material, is stable against reaggregation and can achieve solutions containing exclusively individualized monolayers. Importantly, the charge on the anionic nanosheet solutes is reversible, enables targeted deposition over large areas via electroplating and can initiate novel self-assembly upon drying. Our findings thus reveal a unique solution-like behaviour for 2D materials that enables their scalable production and controlled manipulation.

We report on the self-catalysed growth of vertical InAs(1-x)P(x) nanowires on Si(111) substrates by solid-source molecular-beam epitaxy. High-resolution transmission electron microscopy revealed the mixed wurtzite and zincblende structure of the nanowires. Energy dispersive x-ray spectroscopy and x-ray diffraction measurements were used to study the phosphorus content x in the InAs(1-x)P(x) nanowires, which was shown to be in the range 0-10 %. The dependence of phosphorus incorporation in the nanowires on the phosphorus flux in the growth chamber was investigated. The incorporation rate coefficients of As and P in InAs(1x)P(x) nanowires were found to be in the ratio 10 ± 5 to 1.